TW561186B - Reactive side-chain polymers and their uses - Google Patents

Abstract

The present invention provides novel polyimides, poly(amic acids) and poly(amide esters) thereof, and optical alignment layers derived therefrom, for inducing alignment of liquid crystals and liquid crystal displays. The novel compositions comprise side-chain polymers of the general formula I: -Li-D-L2-Cf, wherein D comprises 1 to 4 carbon-carbon double bonds, Cf is a monovalent C4 to C20 fluorocarbon radical and L1 and L2 are linking groups. The invention further describes liquid crystal displays and other liquid crystal devices.

Description

2. Description of the Invention (1) Background of the Invention The present invention relates to a substance for positioning a liquid crystal, and a liquid crystal optical element. The present invention is implemented by the United States Government under the consent of ARPA Grant No. 8-972-931001. ^ The government has certain rights in the present invention. Current liquid crystal display (LCD) elements include a product using a twisted nematic mode, meaning a structure in which the orientation of nematic liquid crystal molecules is above and below. The electrode substrates are twisted 900, a product that uses the super-twisted nematic mode and uses birefringence, meaning that it has a structure 'where the orientation direction of the nematic liquid crystal molecules is twisted to 300' It is a switching mode on the plane. The two electrodes that control the positioning of the liquid crystal in the substrate are on a substrate, and the orientation of the liquid crystal on the substrate plane <universal 'will change when an electric field is applied. Or antiferroelectric liquid crystal substances. The common feature of each of these products is a liquid crystal layer arranged between a pair of substrates coated with a polymer positioning layer. This polymerization Body: The bit layer controls the orientation direction of the liquid crystal medium in the absence of an electric field. Often, the orientation direction of the liquid crystal medium is established in a mechanical polishing process, where «Polymer M is polished by a cloth or other fiber material. The liquid crystal medium is typically parallel to the mechanical polishing direction = grinding ^ 'can expose the positioning layer containing anisotropic absorption molecules to polarized light, so that the liquid crystal medium is fixed, such as in US Patent 5, G32, _ and 4,974 The method disclosed in "Methods of Positioning and Repositioning Liquid Crystal Media" by using polarized aurora can be used to position the liquid crystal media. It can reduce the accumulation of dust and electrostatic charges in the positioning layer. Possibility. Other advantages of this optical positioning method, including control of positioning direction 561186 A7

System, and the positioning of South Quality. ":" Japanese state "stateless requirements of the optical positioning layer, including the I valve for positioning, for the U water, 4 * brother Youyi deal with clarity (colorless), good dielectric properties and repeated power. Long-term thermal and optical stability, and uniform pre-tilt angle in many applications. "The Da Shaofen night crystal device, including the display, has a defined pre-tilt angle," "controlled by, for example, mechanical polishing of a two-selective polymer positioning layer. The liquid crystal molecules in contact with this layer are aligned parallel to the polishing direction, but are not completely flat on the substrate. The liquid crystal molecules are slightly inclined with respect to the substrate, for example, at about a degree. In Da Shao Fen display, you should pay for the best performance. For the best performance, the limitation of the liquid crystal and the uniform pre-tilt angle are desired. Polymers used to form optical positioning layers must also have reasonably broad processing limits. In commercially available jujube crystal displays, the polymer used as the positioning layer is generally a polyimide-based system because of its good thermal and thermal properties. Therefore, in this polyimide group, the polymer must also have a functional group that is thermally stable and / or chemically imidized. In addition, the polymer must have good wetting characteristics and printability on the substrate to obtain a uniform layer. Several approaches have been explored to meet the performance requirements of optical positioning layers to manufacture liquid crystal displays. In particular, U.S. Patent 5,731,405 describes a polyfluorene imine optical positioning layer having a C4 to fluorinated or partially fluorinated alkyl chain as a side group. These substances can change the surface properties of the optical positioning layer. International application WO 99/15576 describes a photoreactive polyfluorene imine polymer having pendant arylpropionate (cinnamate) groups. When irradiated with polarized light, these substances will be photo-crosslinked 'to produce an optical positioning layer with a limited tilt ^ (Please read the note on the back first to write this page} -Equipped · Consumers ’Cooperative, Intellectual Property Bureau, Ministry of Economic Affairs Printing 5-

561186 A7, one --___ five, description of the invention (3). In this case, establishing a pretilt in the optical positioning layer requires the use of a specific chromophore, such as cinnamate. In the further development of pre-tilt-inducing substances and methods for optical positioning layers, new types of reactive substances have been discovered, which allow the use of chromophores other than cinnamate and the like to control the pre-tilt of the optical positioning layers. Invention Summary 1 The present invention provides a reactive side chain polymer in a class of polyimide, polyamidic acid, and esters thereof, which is characterized in that it contains a monovalent side chain of the general formula: -Lj -D-L2 -Cf where this monovalent link is linked to the polymer main chain, and where: L! And L2 are each a covalent bond or a linking group, selected from _〇_, each,-clothing factory, -〇 · 〇 &gt;, -C0-0-, -n ^ -CO-, -CO-NR``, depending on "Οχ)-, 0-CO-NR", -service 丨 -CO: NR ", and straight chain or branch The chain alkylene group is represented by mono (CH2) n_, -L3- (CH2) n-,-(CH2) n_L3_, _L3- (CH2w), each of which is optionally substituted by gas or gas, and is -〇_ or small chain factory inserted chain, where L3 and L4 are selected from -〇-, _3-, -service 1_, -〇 &lt; 〇_,-(: 〇O -'- NRrCa'.caNRr '. NR ^ cOO-'. Aco.NIV'-NRi- CO-NI ^-, the heart is hydrogen or a lower alkyl group, and η is 1 to 20; D is the second one containing 1 to 4 carbon-carbon double bonds Valence group selected from C3_c24 aliphatic, A · ^ 24 cycloaliphatic, C8-C24 aralkyl, all of which are optionally substituted by 1 to 4 heteroatoms selected from oxygen, nitrogen or sulfur, and optionally by Fluorine, gas or cyano mono- or poly-substituted, Carbon - carbon double bond based η- any other side chain of the isolation system;

Cf represents a valence C4 to C2 0 fluorocarbon group. -6-This paper size is in accordance with Chinese National Standard (CNS) A4 (21〇X 297 mm) (Please read the notes on the back and fill out this page)-Packing. Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 561186 Economy Printed by the Ministry of Intellectual Property Bureau Consumer Cooperatives A7 ______B7 One ____ Five. Description of the Invention (4) The present invention further embodies an optical positioning layer made from a side chain polymer, and a liquid crystal display element incorporating the optical positioning layer . Brief Description of the Drawings Fig. 1 illustrates an optical system for exposing a substrate to UV light. FIG. 2 is a cross-sectional view of an LCD device according to the present invention. Figure 3 illustrates the synthesis of novel side chain aromatic amines. Detailed description The term "positioning layer" as used herein refers to a material layer on the substrate surface, which controls the positioning of the liquid crystal layer in the absence of an external electric field. Here, the conventional positioning layer π means a positioning layer that positions the liquid crystal layer only by processing other than optical processing. For example, mechanical polishing of polyimide, evaporated silicon dioxide, and Langmuir-Blodgett films have all been shown to position liquid crystals. Here, the 'optical positioning layer' refers to a positioning layer containing molecules which are absorbed in an anisotropic manner, which will induce the positioning of liquid crystals after exposure to polarized light. This optical positioning layer may be An isotropic medium may have a certain degree of anisotropy. The optical positioning layer can be processed by conventional methods, such as mechanical friction, before or after being exposed to polarized light. The optical positioning layer t molecules absorbed in an anisotropic manner, When measured along axes in different directions, they show absorption properties with different numbers. This anisotropic absorption molecule shows an absorption band between 150 nm and about 2000 μm. The optimal optical positioning layer of the present invention has The maximum absorption is about 150 to 400 nanometers, and especially about 300 to 400 nanometers. The polymer which is particularly useful and preferably used as an optical positioning layer is polyfluorene ^ 1 1 — nnn I · n ii (Please read the note on the back first to write this page) -L. v ^ l · · -line · This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 6 6 8 Α7R7 Ministry of Economic Affairs Wisdom Property bureau member Printed by the Industrial and Commercial Cooperatives 5. Description of the invention (5) · Amine. Polyimide is known to have superior thermal and electrical stability properties, and these properties can be used in the optical positioning layer of liquid crystal displays. Preparation of polyimide is described In 'Polyimine', edited by D. Wilson, HD Stenzenberger and PM M. Hergenrother, Chapman and Hall, New York (1990). Polyimide is typically made by condensing ~ equivalent diamine and one equivalent of dianhydride in a polar solvent to obtain a poly (St-amine) prepolymer intermediate. The polyfluorene imine copolymer is made by condensing one or more diamines with one or more dianhydrides to obtain a copolyamine. An alternative intermediate of polyimide is poly (amidate), which can be formed by the esterification of poly (amidate) and alcohols. This poly (amidate) is thermally imidized to form a polyamidate. Therefore, the 'poly (Sf amine) and poly (amidate) systems are considered to be closely related precursors of the polymer imine of the present invention. Therefore, they are considered to be other specific embodiments of the present invention. Furthermore, the chemically or thermally imidized polyimide derived from poly (amidate) or poly (amidate) is also considered as a specific embodiment of the present invention. . The novel polymerization system of the present invention is a reactive side chain polymer in the class of polyimide, polyamidic acid and its esters, which is characterized in that it contains a monovalent side chain of the general formula J:

Lj -D-L2 -Cf I where this monovalent link is tied to the polymer backbone, and where:

Li and L2 are each independently a covalent bond or a linking group, and are selected from the group consisting of s ·, _ 1-, -O-CO-, -CCMD-, -CO-NR "'-NRrCO-a, .Θ-CaNRi -, -NRi -CO-NRi-, and linear or branched chain alkylene groups, _ This paper is applicable to Zhongguanjia Standard (CNS) A4 specification coffee 297 issued) Ί-) ----- ----- C Please read the notes on the back and fill in this page first) Order: 561186 A7 B7 V. Description of the invention (6 Printing of clothing by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy (^ ¾) n-, -L3-( CH2) n-,-(CH2) n -L3-, -L3-(CH2) n -L4-means that each is optionally mono- or poly-substituted by fluorine or chlorine, and is optionally -0_ or -NR1 _ Inserted chain, where L3 and L4 are selected from seven ... each, ...! ^-,-^^-, · ^ -α ^ -NR ^ CO- ^ -CO-NRj. &Gt; -NRj-CO-O- ^ -O-CO-NR!-&Gt; CaNRi ·, Ri is hydrogen or lower alkyl, and η is 1 to 20; is a divalent group containing 1 to 4 carbon-carbon double bonds, selected from c3 -C24 aliphatic, A- ^ 24 cycloaliphatic, c8-C24 aralkyl, all are optionally substituted with 1 to 4 heteroatoms selected from oxygen, nitrogen and sulfur, and optionally fluorine, chlorine or cyanide Mono- or poly-substituted, in which the carbon-carbon double bond system and the side Any other π_ system isolation; cf represents a unit price (: 4 to (: 20 fluorocarbon groups. Π chain inserted by 〇- or -NRi "), meaning in the straight or branched chain One or more carbons in the fe group are formally replaced by 0- or _NR1. Preferably, h and L2 are covalent bonds, _〇 · and -NRi ·. The term "low-carbon alkynyl" means Straight-chain and branched saturated hydrocarbon groups, having 1 to 6, preferably 1 to 4 carbon atoms, such as methyl, ethyl, or isopropyl, etc. '' Low-carbon alkoxy, means attached to oxygen Identical hydrocarbon groups linked to an atom. &Quot; Lower fluoroalkyl group &quot; means the same hydrocarbon group mono- or polysubstituted by fluorine., &Quot; lower fluoroalkoxy group &quot; The same hydrocarbon group. Refer to "D", "c ^ C24aralkyl", which means an organic group containing an aryl group and an alkyl group or an aryl group and an alicyclic group. An example of the former is a phenyl group. Butyl: 3-phenylpentyl, etc. Examples of the latter are phenylcyclohexyl, di'tetrahydrofluorene, etc. "Substituted by optionally from 4 to 4 heteroatoms selected from oxygen, nitrogen or sulfur" ,system ‘Means one to four carbons in an aliphatic alicyclic or aralkyl group (please read the notes on the back first and fill in this page) 丨

561186 A7 B7 In the fifth, the description of the invention (7 atoms, can be formally set to two volts by oxygen, nitrogen or sulfur. For example, in a stupid ring a carbon is replaced by nitrogen, which means ton%. In 2- Cage: the two carbons of a certain D and φ are replaced by nitrogen, which means T-based ethylamine benzene., Any other Π-system isolation in the side chain of the toilet "^ + y P It is said that the carbon-carbon double bond is not directly conjugated to another Π- system, such as Guan ... # 10,000 rank frame (such as stilbene), carbonyl (such as acrylate) or a combination of both (such as Cha. The preferred D system has 1 to 2 carbon-carbon double bonds and is substituted by (^ heteroatoms (C3-C1G aliphatic or aryl aryl). The preferred D part series is shown in "Best. D part A wide variety of structural variants are possible in the substituent-2 · propenyl and M • substituted_2 · butenyl moieties D. "Reactive" -㈣ does not mean to limit the side chain polymer #specific effect Mode. Rather, the term is intended to suggest how a technician polymer can perform its function. It is speculated that the double bond in the D group can provide reactivity, allowing during exposure to polarized light / Or later, change in the side chain chemical environment. This change can be due to bond formation, bond breakage, isomerization or some D groups can also act as polarizable functional groups, which will interact with the polymer medium Other anisotropic dipole interactions. In any case, the present invention is not limited to a specific mechanism of action. 'With reference to the Cf group, the phrase "monovalent q to (: ⑼fluorocarbon group" means ^ to C2 〇 Saturated and unsaturated, linear and branched alkyl, cycloaliphatic, aryl and aralkyl hydrocarbon groups, which are mono- or poly-substituted by fluorine. Examples of fluoroalkyl groups are: 1H, 1H_pentadecafluorooctyl , 1H, 1H, 10H-octadecanefluorodecane, 2- (perfluorohexyl) ethyl, perfluorohexyl, perfluoroheptyl, perfluorooctyl, perfluorononyl, and peroxoamyl. Examples of cyclic groups are perfluorocyclopentyl and perfluorocyclohexyl. Fluoroaryl 10- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the note on the back first (Fill in this page) 丨 Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 561186 A7

V. Explanation of the invention (8) Examples of pentafluoro and octafluoroqinyl. An example of an arsenyl group is perfluoro · 4-methylphenyl. The preferred Cf group has 6 to 20 carbon fluorides, and the most preferred group has 8 to 20 carbon fluorides. Preferred Cf groups include perfluorohexyl, perfluorooctyl 1H, 1H, 2H, 2H-perfluorooctyl and 1H, 1H, 10H-perallyl decyl. Most preferred are 1H, 1H-perfluorooctyl and 1H, 1H, 2H, 2H-perfluorooctyl. The preferred polyimide, polyamidic acid, and polyamidate of the present invention are side-chain polymers, wherein the main chain of the polymer contains the same or different repeating groups, and is selected from one or more of the following general formulas, 0 0

bo2〆, C〇2B | Alb L Factory Dq—Cf (please read the notes on the back * ^ fill out this page)-installed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs where M is a tetracarboxylic dianhydride. The four-valent organic group after the two groups' has four valence bonds distributed between the four different carbon atoms of the group; A is trivalent unsubstituted, or optionally fluorine-, gas-, Cyano-, lower alkyl-, lower alkoxy-, lower fluoroalkyl- or lower fluoroalkoxy substituted aromatic or cycloaliphatic groups; and B is hydrogen, or in the form After removal of the hydroxyl group, a monovalent organic group derived from an alcohol. The preferred M is a diaryl ketone of the following formula ♦ -11-This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 561186 A7 B7 V. Description of the invention (9 0. 1 (2 FREE \ Where Ar is unsubstituted 'or optionally substituted by gas, trifluoromethyl- and cyano (aromatic system, selected from five, six, nine, and ten carbon systems, of which one, two, or two carbons Is replaced by a heteroatom selected from · α, _N_ and _s •; z and m are described below. Preferred Ar systems are selected from phenyl, pyridyl, pyrimidinyl, naphthyl and benzene Thio. More preferably M is a diaryl ketone of the formula

, -S02-, -CH2 _, -C (CF3) 2 ... -C (0)-, -CH2 CH2 ·, -NRi-and covalent bonds, wherein Ri is selected from H or lower alkyl; m is 1 or 0; and a is selected from y

i / l --- r -------- install --- (Please read the notes on the back first and fill in this page) · • Line! Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs where X! Is selected from the group consisting of Η, F, Cl, -CN, lower alkyl, lower alkoxy, lower fluoroalkyl or lower fluoroalkoxy. Preferably A is a substituted or unsubstituted trivalent phenyl group, and most preferably is an unsubstituted trivalent phenyl group, which means that X1 is hydrogen. Preferred polymers of the present invention are those in which m is 0 and X is Η or C1. It is derived from 3,3 ·, 4,4 · -benzophenone tetracarboxylic dianhydride and 2,2, -dichloro-4,4,5,5, -benzophenone tetracarboxylic dianhydride. Both substances are colorless, provide reasonable solubility characteristics for polyamic acid, and provide a photoactive UV chromophore. Very good side chain polyimide contains -12 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 561186 A7 B7 V. Description of the invention (ι〇) Repeat unit

These benzophenone tetracarboxylic dianhydrides are readily available from commercial sources or synthetically. For example, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride (BTDA) is available from Yachichi Chemical Co. (1001 W. St. Paul Ave., Milwaukee, WI 53233). 2,2, -Digas-4,4,5,5,5, -benzophenone tetracarboxylic dianhydride can be obtained from 4_Ga-Zheng xylene, through Friedel-Cmfts dehydration with gasified grasshopper To obtain 2,2, _digas_4,4,5, tetramethylbenzophenone, followed by oxidation with nitric acid and dehydration of the formed tetracarboxylic acid, such as Falcigno et al., J. P 〇ly. Sci · 1992, 30, 1433 Other diaryl ketone dianhydrides which can be used in the method of the present invention, wherein 111 is 1, is a polycyclic ring described by Pfeifer et al. In US Patent No. 4,698,295. Diaryl ketone dianhydrides are incorporated herein by reference. A wide variety of other dianhydrides can of course be used to form copolymerized fluorinated acids. Specific examples of other tetracarboxylic monoanhydride components include aromatic dianhydrides, such as pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, ι, 2 ,, 5,6-fluorenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetrakidianhydride, 3,3'4,4'-biphenyltetracarboxylic dianhydride, 2,3,2,, 3, -Biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) monoepifluorene dicellulose, bis (3,4-diplex Phenyl) methylene di liver, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis ( 3,4-dicarboxyphenyl-) propane dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, 2,3,4,5-pyridine tetrabenzate; alicyclic Four-to-two traits, such as 1,2,3,4- Butter-fired four-to-two fiber -13- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the note on the back first Please fill in this page)-Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 561186 A7 B7 V. Description of the invention (11): u, 3, 4-cyclobutane tetra #m, 3, 4 cyclopentyl tetracarboxylic n, 4,5_ Hexane tetramethylene monoanhydride, 2,3,5-dicarboxycyclopentylacetic dianhydride And 3,4_dicarboxyl Tetrahydrotetrahydro + teastilate and its acid and gasification derivatives. The optimal polyfluorene imide of the present invention requires a new lysed aromatic diamine of the following structure

Printed by the Consumer Goods Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the L Plant. L2 L2, D, and Cf have the same meaning as described above. Preferred aromatic diamines are 4-substituted-U-phenylenediamine and 2-substituted · M-phenylenediamine, with substituents in the fluorene horse-h-D-q-q side chain. The most preferred diamine is 2-substituted, 4-phenylenediamine. In general, the novel aromatic diamines can be easily prepared by the process outlined in FIG. 3. The starting materials are fluorinated or partially fluorinated fresh, amines or thiols, which are treated in the presence of excess dioxide Bγ-D-Bi. Response at all positions. Removal of excess bimetallic compounds' yields the secretion of the monomolybdenum intermediate. This monoaluminium compound can be treated with, for example, dinitrophenol (L plant H = 0H) and alkali to obtain a dinitroaromatic compound, which can be obtained when treated with gasified tin (Π). An aromatic diamine is needed. Alternatively, the monobromide intermediate L2_c # h_Vh can be treated, such as water, a higher aliphatic amine, or hydrogen sulfide, to produce an intermediate called 〇〇2 &amp;. H_Li-D-L2-Cf is further treated with, for example, dinitrofluorobenzene and a base to obtain a dinitro aromatic compound. Alternatively, the dinitrophenol may be alkylated with excess dibromide Br_D_Br. The formed mono-molybdate can be treated with fluorinated or partially gasified alcohols, amines or hard alcohols to produce dinitroaromatic compounds. You can use these two original papers ~ National · National Standard (CNS) A4 specifications ⑵〇x 297 public love (please read the notes on the back to fill out this page)-installed · '561186 A7 V. Description of the invention (12) The compounds Br-D-Br are replaced with other dihalogenated 'hostilities', such as the digases C1-D-C1. Instead of dinitrofluorobenzene, you can use other dinitronanguan fines .., produced # 丞 固 冬 类, such as dinitrochlorobenzene. Furthermore, nitroanilides can be used instead of dinitrodentate, as exemplified in the examples. Monofunctional fluorinated and partially gasified alcohols are commercially available. For example, m, 1H, 5H_octafluoropentyl alcohol, 1Η, 1Η_perfluoro-1-octanol, 1Η, 1Η, 2Η, 2Η-perfluorooctanol, 1Η, 1Η-perfluoro_ 丨 decanol, 1η, 1Η, 2Η 2η, perfluoro_1decanol, 211-perfluoro-1-dodecanol, 2 ° C, commercially available from 〇〇〇〇 (; 1 Product Company (West Cobmbia, SC 29169) Several other substances can be obtained by the reduction of the corresponding acid or gaseous plutonium using the procedure in Maaomd. Chem. Phys., Chi, 1021_1029 (1966). Primary and secondary amines are easily obtained by reduction of the corresponding amines and diborane in tetrahydrofuran. Table 2 lists examples of preferred diamines. Examples 丨 _9 describe their synthesis, and general It exemplifies the synthesis of novel diamines. A variety of other diamines can be used to prepare the novel copolymerized fluorene imines of the present invention, including aromatic diamines, such as 2,5 · diaminobenzonitrile, ^ trifluoromethyl Phenylenediamine, p-phenylenediamine, 2-amino-1,4-phenylenediamine, 2-fluoro-1,4-phenylenediamine, m-phenylenediamine, 2,5-diaminotoluene , 2,6-diaminotoluene, 4,4 · -diaminobiphenyl, 3,3f-dimethyl -4A · diaminobiphenyl, 3,3, -dimethoxy-4,4, -diaminobiphenyl, diaminodiphenylmethane, diaminobiphenyl ether, 2, 2-diaminobiphenylpropane, bis (3,5-diethyl-4-aminophenyl) methane, diaminodibenzylsulfone, diaminofluorene, 1,4-bis (4-amine Phenoxy) benzene, 4,4, -diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-bis (4-aminophenyl) benzene, 9, 10-double (4- 15-) This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the notes on the back first and fill out this page) Printed by the cooperative 561186 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _____B7 One __ V. Description of the invention (13). , 4,4'-bis (4-aminophenoxy) monophenyl, 2,2_bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis ( 4-aminophenyl) hexafluoropropane and 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane; cycloaliphatic diamines, such as bis (4-amine Cyclohexyl And aliphatic diamines such as butanediamine and hexamethylenediamine. Furthermore, diaminosiloxanes such as bis (3-aminopropyl) tetramethyldisiloxane can be used. Diamines can be used alone or in combination of two or more of them. The preferred diamines used to prepare the copolymerized fluorene imines are 2,5-diaminobenzonitrile, 2- (trifluoromethyl) 1,4-phenylenediamine, 2- (N, N-diallylamino, H, 4-phenylenediamine, diallylamino) -2,4-phenylenediamine and ι, 4 -Phenylenediamine. More preferred diamines are 2,5-diaminobenzonitrile, 2- (trifluoromethyl) -fluorene, 4-phenylenediamine, and 2- (N, N-dimethylaminopropylphenylphenylamine. The novel polyimide and copolyimide of the present invention preferably contain 5 to 100 moles, and more preferably 20 to 90 moles. The side chain repeating unit is prepared in When using polyamic acid for optical positioning layer, the molar ratio of diamine to dianhydride is usually 1: 1, but it can be changed between 0.8: 丨 and 12 · · 丨. The preferred ratio is between 0.9: 1 and u: 丨. To prepare an optical positioning layer, a poly (fluorenic acid) solution or a preimidized polyimide solution is coated on the desired substrate. Coating is usually achieved with 2 to 30 weight solids. Any conventional method can be used to coat the substrate, including brushing, spraying, spin casting, meniscus coating, dip coating or printing. In the examples Demonstration of the preferred technology for coating substrates is rotation and printing. However, the optical positioning material of the present invention is not limited to use in printing or spinning methods., '-16- This paper size_ 巧 _standard CNS) A4 secret (21〇7i7 ^ F) (Please read the notes on the back to fill out this page first) -Installation · 'Α7 B7 V. Description of the invention (M, in an oven' under an inert atmosphere, such as nitrogen or argon Two times 'usually no more than boots, and is preferably at or below 2 hours' is preferably about 2 hours or less. This addition procedure is to remove the solvent carrier, and you can use ^ you take. 1 文 来 口Coarse and further mature. For example, ris =) The film is thermally cured to produce a polyimide film. The choice of degree and solvent can affect the optical positioning quality, pretilt: and: pressure retention ratio (VHR). For example It has been found that when the concentration of the polymer decreases in the medium, the optical positioning quality will be improved under the same exposure. The choice of :: 丨 and / or co-solvent can also affect the positioning quality. In the film thickness-舁 疋The interrelationship between the dimensional qualities is also significant. In particular, the optical positioning quality will be improved as the thickness is reduced. Similarly, the VHR system will be increased as the film thickness is reduced. The optical positioning layer is exposed to polarized aurora, To induce liquid crystal positioning. The so-called &quot; polarized light &quot; means light ellipse Ground and / or partially polarized so that light is more polarized along one axis (called the long axis) than the orthogonal axis (called the short axis). F In the present invention, polarized aurora has one or more The wavelength is from about 150 to 2 nanometers, and preferably about 150 to 1600 nanometers, and more preferably about 150 to 800 micrometers. The best polarized light system has one or more wavelengths, from about 150. To 400 nm, especially about 300 to 400 nm. Preferred light sources are lasers such as argon, helium neon or helium cadmium. Other preferred light sources are mercury arc deuterium and quartz tungsten halogen lamps, gas lamps, microwaves Excitation lamp and black light with polarizer. It can be used to generate polarized light from non-polarized light source. It is an interference polarizer, absorptive polarizer, diffraction grating and Brewster reflection based on dielectric stack. Reflective polarizer. Use lower power laser or when making small positioning-17 This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (Please read the notes on the back first and fill in this page) Printed by the Consumer Cooperative of the Property Bureau 561186 A7 ------ B7 '______ V. Description of the invention (15) · When the area is full, it may be necessary to focus the light' beam on the optical positioning layer. The so-called 'exposure' means that polarized light is applied to the entire optical positioning layer or to the surface. This beam can be fixed or rotated. Exposure can be performed in a single step in a continuous shot 'in a scan mode or by other methods. The exposure time varies widely with the substance used, etc., and can range from less than 1 leap second to more than 1 hour. The exposure may be performed after or after the optical positioning layer is brought into contact with the liquid crystal medium. Exposure can be achieved through linear polarized light, passing through at least one patterned cover, or using a linear polarized light beam scanned over a pattern. Exposure can also be achieved using interference of coherent beams to form a pattern ', which means alternating dark and light lines. The amount of exposure energy required varies with the formulation of the optical positioning layer and the processing before and during exposure. A preferred range of exposure energy is about 0.001 to 100 joules / cm2, and an optimal range of exposure energy is about 0.001 to 5 joules / cm2. Lower exposure energies are most useful for large-scale fabrication of optical positioning layers and liquid crystal display TF device elements. The lower exposure energy also minimizes the risk of injury to other substances on the substrate. The quality of the positioning and electrical properties of a liquid crystal cell assembled from an exposed substrate can be improved by heating the substrate after exposure but before assembly, and / or filling the cell. This additional heating of the substrate and / or unit is not a requirement of this process, but it can give favorable results. The application of the liquid crystal medium to the optical positioning layer can be achieved by capillary filling of the unit, the cast film of the liquid crystal medium on the optical positioning layer, the lamination of a preformed liquid crystal film on the optical positioning layer, or other methods. A better method is to optically position the capillary filling, injection filling and antimony film of the liquid crystal medium (please read the precautions on the back first> ^^ Fill this page).

561186 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 __B7 I_ V. Description of Invention (16). * On the layer. The optical positioning layer is exposed to polarized light in advance, or is exposed after contacting the liquid crystal medium. A unit can be made using two coated substrates to provide a sandwich-like layer of a liquid crystal medium. This substrate pair may each contain an optical positioning layer, or a conventional positioning layer (for example, mechanically polished) may be used as a second positioning layer containing the same or different polymers. As a liquid crystal substance used for a liquid crystal optical element, a nematic liquid crystal substance, a ferroelectric liquid crystal substance, etc. can be used. The liquid crystals that can be used in the present invention described herein include positive dielectric liquid crystals, including 'cyano-4f-alkylbiphenyl, 4-cyanoalkoxybiphenyl, 4-alkyl- (4'-cyano Phenyl) cyclohexane, 4-alkyl- (4f-cyanobiphenyl) cyclohexane, 4-cyanophenyl-4'-alkylbenzoate, 4-cyanophenyl- 4'-alkoxybenzoate, 4-alkoxyphenyl-4'-cyanobenzoate, 4-alkylphenyl-4 · -alkylbenzoate, (-( Each alkylphenyl) -4-cyanopyrimidine, 1- (4'-alkoxyphenyl) -4-cyanopyrimidine, and 1- (4-cyanophenyl) -4-alkylpyrimidine. Others Usable liquid crystals are novel superfluorinated liquid crystals, available from EM Industries (Hawthrone NY), including commercially available materials: Zυ-5079, Zυ-5080, ZΠ-5081, ZΠ-5092, ZΠ-4792, ZLI_1828, MLC- 2016, MLC-2019, MLC-6252 and MLC-6043. Other usable nematic substances for implementing the present invention, including commercially available liquid crystals available from Lodic (Tokyo, Japan), including DLC series: 22111 , 22112, 22121, 22122, 23070, 23170, 23080, 23180, 42111, 42112, 42122, 43001, 43002, 43003, 63001, 63002, 63003, 63004, and 63005. Polymerizable liquid crystal monomers can also be used in the present invention. Preferred are those disclosed in US Patent No. 5,846,452, and are incorporated herein by reference. The present invention is not limited to the use of liquid crystals as defined above. Those who are familiar with this art will ___ -19- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the notes on the back first_Fill this page) -Packing · V. Description of the invention ( 17) It is clear that the present invention is valuable when using a variety of liquid crystal structures and formulations containing liquid crystal mixtures. The exposed optical positioning layer will meet the liquid crystal medium, and the linearity of the incident light beam in the eyes The polarization direction and the plane along the optical positioning layer are at the angle of + and _Θ. The artist will understand that this method allows the liquid crystal medium f to be controlled in the optical system by controlling the conditions of polarized light exposure. The level of the bit layer: inside 'is positioned in any desired direction. Therefore, the range of Θ can be from 0 to 180 for the polarization direction. The liquid crystal display element of the present invention is composed of a polymer having at least one side chain. Amine optical positioning layer The electrode substrate, the applied voltage setting, and the liquid crystal material composition. Figure 2 illustrates a typical liquid crystal display element, which contains indium-tin oxide) or tin oxide transparent electrode 13, on the substrate ΐ2, and the optical formed on ^ Positioning number 14. Exposure of the optical positioning layer to polarized light has the name "one or more wavelengths" in an absorption band that absorbs molecules in an anisotropic manner. The interstitial material 15 accompanied by the sealing resin is inserted into a pair of optical positioning: 14 (interval. With the capillary filling of the unit, the liquid crystal 16 is applied, and the element is sealed to construct a liquid crystal display element. The substrate 12 may include an outer Thin coatings such as insulating films, ocher films, color filter overcoats, laminated polarizing films, etc. These coatings and films are considered to be part of the substrate 12. Furthermore, 'King moving components' For example, thin-film transistors, non-linear resistance elements, etc. can also be formed on the substrate 12. These electrodes, undercoats, overcoats, etc., are components for f of night crystal displays, and can be used in this In the display element of the invention, the electrode substrate and the n-crystal display unit thus formed are used, and the liquid crystal is filled in the gap towel of the child unit to prepare a liquid crystal display element 561186 A7 --------- B7 5. Description of the invention (18) pieces, and the voltage setting is used in combination. The optical foot layer of the present invention is compatible with all liquid crystal display modes. The liquid crystal display element of the present invention may include multiple display types, including twisted nematic Supertwisted nematic On-plane switching, vertical positioning, active matrix, cholesterol, polymer dispersion, ferroelectric, antiferroelectric, and multi-function LCD monitors. Although the display modes exemplified in this patent specification are mainly twisted nematic, However, the optical positioning layer of the present invention is not limited to use in a twisted nematic liquid crystal display. The optical positioning layer of the present invention can be used in many other liquid crystal devices other than the liquid crystal display. It includes an electro-optic light modulator, all-optical light Modulators, erasable read / write optical data storage media; diffractive optical components such as gratings, beam splitters, lenses (such as J: resnel lenses), passive imaging systems, Fourier processors, optical discs, and radiation collimators; Binary optical devices formed by combining refractive and diffractive optical devices include glasses, cameras, night vision goggles, robot vision and stereoscopic image viewing devices; and holographic devices such as head-up displays and optical scanners. Some examples use 1- (N, N-diallylamino) · 2,4-phenylenediamine as a comonomer. This substance Prepared as follows: 2,4-dinitrofluorobenzene (9.3 g), N-methyltetrahydropyrrolidone ^ Mρ,% ml), diallylamine (5.82 g), and potassium carbonate (6.9 g ), Stir at ambient temperature for 1 hour. The mixture was poured into water and extracted with ether. The extract was washed twice with water, once with a saturated saline solution, and slowly dehydrated and dried with stone J5L acid. The annual solution was concentrated to obtain N, N-diallyl_2,4_dichofuraniline as a yellow oil (14.6 g). -21-^ This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) '---- (Please read the note on the back first to complete this page) 丨 Install I' Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the employee consumer cooperative 561186 A7 B7 -__ _ V. Description of the invention (19). · The above yellow oil (14.6 g) was gasified with tin tin dihydrate (900 g), 10 Ν hydrochloric acid (75 Ml) and ethanol (250 ml) solution at 55-6. ○ treatment 14.5 hours. The mixture was poured into ice water and weighed on a cold basis. ,. Hydroxide solution (750 g) was tested. The mixture was extracted with Otto, and the extract was washed with water. The strip was washed twice with a saturated saline solution and dried (MgS04). The mixture was purified by chromatography, followed by Shixi Dangtu steaming hall (115-12 ° C, 0.01 mm Hg) 'to obtain 1- (N, N- allylpropylamino) · 2,4-phenylenediamine as a yellow oil. 1 H NMR (CDC13) 6.79 (d, 1Η), 6.08 (m, 2Η), 5.80 (m, 2Η), 5.10 ⑽ 4Η), 3.45 (dt, 4Η), 4.0 (bs), and 3.5 ( bs). In the entire example regarding the procedure using NMP, and the procedure using vaporized tin (II) dihydrate, the above-mentioned extraction, washing and drying procedures are repeated several times. Its system is called &quot; Extraction in a general way &quot;.纟 Examples: When preparing polydonkey acid, make NMP and r-butyrolactone self-hydrogenated before use (please read the notes on the back first and fill in this page). r -22- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 561186 A7 B7 Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (20) Table 1. In the present invention The preferred D-group used in side chain polyfluorene imine—CHjCHCH—

2CH = CH2’CI ^ CHCHC%

Qr \ ICI ^ CHCHCH ^ Person-23- -n fi ϋ ϋ n ϋ n ϋ n · .1 nn I · · ϋ n (Please read the notes on the back first and fill in this page) This paper size applies to Chinese national standards (CNS ) A4 size (210 X 297 mm) 561186 A7 B7 15. Description of the invention (21) Table 2. Examples of aromatic diamines with reactive side chains Diamine numbering structure

N Eight A CH C F

n ^ -ALJ / -nh2

Me ^ N.

N

NHL, 0 15, C6p13 (Please read the notes on the back first '^ Fill in this page) Pack I. N Eight C F.-Line · Public clothing printed by the employee ’s consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

N ^)-CsF. Cy

CH, 'A

CH = CH 2 24-This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 561186 A7 V. Description of the invention (22 Table 2 (continued) Number of diamines Structure

(Please read the notes on the back to fill in this page)-丨

9 9 丨 3_ Only households ^ NHj The following examples are intended to illustrate specific embodiments and are not intended to limit the scope of the invention. Example 1 The following example describes the synthesis of a novel aromatic diamine 1. 1H, 1H perfluorooctanol (30.0 g, 0.075 mole), i, 4-dibromo-2-butene (48.0 g, 0.25 mole), Aliquat 336 (1.5 g), toluene (150 ml) and a mixture of potassium hydroxide (0.075 moles, 4.95 g) in water (50 liters), heated to 80-90 C for 3 hours. The mixture was extracted with water-diethyl ether. The extract was washed twice with water, washed with a saturated sodium gas solution, dehydrated and dried (MgS04) and reduced to oil. The excess dibromide was removed via recrystallization in hexane. Make * &quot; &quot;-25-The scale is closed at the right time, and the family is in good order.) ---- 1 ^ 'I. • Line · 561186 A7 B7 V. Description of the invention (23) · Residual oil via diatom Soil distillation (0.1 mm Hg, 70-95X :) to obtain 28.0 g of 1-bromo-4- (1Η, 1Η-perfluorooctyloxy) -2 · butene. 1-bromo · 4- (1Η, 1Η-perfluorooctyloxy) _2-butane (28.0 g) was added to 40 weight. /. Amidine (59 ml), tetrahydrofuran (60 ml) and ethanol (40 ml) were mixed at 40 ° C, and the mixture was stirred at ambient temperature for 2 hours. Place the mixture at 20 weight. ^ Basic potassium hydroxide (KOH, 15 g) was basified, extracted, concentrated and distilled to obtain 18.0 g of 1- (N-methylamino) -4- (1Η, 1Η-perfluorooctyloxy) -2- Butene (0.1 mm Hg, 85-11 CTC). 1- (N-methylamino) -4- (1Η, 1Η-perfluorooctyloxy) -2-butene (17.3 g), 3-fluoro-4-nitroaniline (5.46 g), A mixture of triethylamine (7 ml) and NMP (80 ml) was heated at 80-90 ° C for 16 hours. The mixture was extracted in a general manner and purified by chromatography to obtain 15.6 g of 3-substituted nitramine. Nitromine (15.2 g, 25, millimoles) was gasified with tin (II) dihydrate (24.6 g, 0.11 mole), 10N hydrochloric acid (20 ml), and ethanol (200 ml) at 40-45 ° Treated at C for 16 hours. The mixture was diluted with cold water to 20 weight alpha. KOH (220 g) was basified and extracted in the usual way. Purification and crystallization on silica gel to obtain diamine 1 (melting point 46-47 ° C). Example 2 The following example describes the synthesis of a novel aromatic diamine 2. N-methyl-N'-methyl-1,4-diamino-2-butene (3.42 g, 30 mmol), 3-fluoro-4-nitroethylanilide (1 · 5 g 15 mmol) and acetonitrile (10 ml), heated to 70 ° C for 3.5 hours. The mixture is extracted in the usual manner 'and concentrated to an oil. This oil (1.75 g, 6 mmol) was used as the source of C-1, 21 to 1,211-perfluorooctane (3.13 g, 6.6 mmol), &gt; ^? (10 ml) and ___ -26- A paper size is applicable to China National Standard (CNS) A4 (21 × 297 mm) ---- ^ --------- Agriculture --- (Please read the back first (Notes to fill in this page). 丨 Line · Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 561186 A7 _____B7 '__ V. Description of the Invention (24). · Potassium carbonate (L24 g) is processed at 60 C for 16 hours. The mixture was extracted in a general manner and purified by chromatography to obtain 2.2 g of the corresponding acetanilide. This acetoaniline (2_2 g, 3.4 mmol) was mixed with ethanol (42 ml) and 20 weight. . Sulfuric acid (18 mL) was heated to reflux together for 2 hours. The mixture was basified with potassium hydroxide (36 g, 20 wt.%), Extracted in a general manner, and purified by chromatography to obtain 1.6 g of the corresponding nitramine as an oil. This nitramine (1.60 g, 2.7 mmol) was used to vaporize tin gadolinium dihydrate (3.0 g, 13.4 mmol), 10 N hydrochloric acid (1.6 ml), and ethanol (20 ml) at 40- Process at 45 ° C for 2 hours. Place the mixture at 20 weight. . KOH (26 g) was basified and extracted in a general manner and purified by chromatography to obtain diamine 2 (0.71 g, melting point 42.5-44.5 ° C). Example 3 The following example describes the synthesis of a novel aromatic diamine 3. Add 2,4-dinitrofen (5.18 g), 1-bromo_4_ (ih, 1H_perfluorooctyloxy) · 2-butene (10.0 g), potassium carbonate (5.18 g) And NMP (50 ml), heated to 50 C 'for 24 hours. The mixture was extracted in the usual manner, except that the crude extract was first washed with dilute potassium hydroxide. The organic phase gave an oil (97 g). This oil (9.7 g) was treated with vaporized tin rhenium dihydrate (27.5 g), 10 v hydrochloric acid (24.4 ml) and ethanol (140 ml) at 25-35 ° C for 16 hours. The mixture was diluted with water to 20 weight. . KOH (245 *) was basified and extracted in a general manner to obtain diamine 3 (2.90 g, melting point 48_5-50.f C) by chromatography. Example 4. The following example describes the synthesis of a novel aromatic diamine 4. And '(] King Fluoro-n-octyl) propan-2-ol (2.85 grams of Oakwood product) at ρ ratio bite ^ Paper size applies + four or four private standard flat UJNS) A4 specification (21〇X love) --- -(Please read the note on the back 3 and fill in this page first) Equipment · Printed clothing by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 561186 A7 B7 V. Description of the invention (25). · (3 亳 liter) Tosylate (2.85 g) was treated in pyridine (6 ml) at 0-5 ° C for 6 hours. The mixture was diluted with cold water, extracted twice with cold ether-tetrahydrofuran (4.1.1), and washed with cold 2N hydrochloric acid. It was further washed with water, brine, and dried (Na2SO4), and then concentrated to obtain its corresponding tosylate as a solid (2.9 g). This tosylate (3.9 g) was added at 40% by weight. Methylamine (6.4 ml), ethanol (6 ml) and tetrahydrofuran (12 ml) were treated at ambient temperature for 4 hours. Extracted by age, washed with water and saline solution, dehydrated and dried with MgSO4, and distilled through diatomaceous earth (80-100 ° C, 0.01 mm Hg) to obtain 2.7 g of N-methyl- (3-total-n-octyl) propan-2-oxamine. Add the above N-methyl- (3-perfluoro-n-octyl) prop-2-enamine (2.6 g) to 3-fluoro-4-nitroaniline (0.62 g) and triethylamine (1.2 ml) and NMP (6 ml) were treated at 60-65 C for 16 hours and at 80-90 ° F for 23 hours. The mixture was extracted in a general manner and purified by chromatography to obtain 3_substituted_4-nitroaniline as a yellow solid. The above yellow solid (3.3 g) was treated with gasified tin (Π) dihydrate (5.95 g), ethanol (40 ml) and 10 N hydrochloric acid (4.2 ml) at 35-40 ° F for 18 hours. The mixture was diluted with water and basified with 20 wt% KOH (52 g), extracted in a general manner 'and purified by chromatography to obtain diamine 4 (11 g, melting point 62-65.). Example 5 The following example describes the synthesis of a novel aromatic diamine 5. A modified procedure was used by McLoughlin et al., Tetrahedron, Asia, 592 (1% 9). Therefore, '17 g of green steel powder (Aldrich), perfluoro small iodooctane (13.5 g), and 'distillate one methyl arsenal (40 ml) were heated to 1 l0-120 ° C, 28- (Please read the note on the back of the page to fill in this page first)-Install I. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 97 2 X ο 21 Code 4 A 1 / η IN J IV Dry "561186 A7 B7 V. Description of the invention (26) After 3.0 hours, 3-iodoaniline (4.92 g) was added. The mixture was stirred at 100-110 ° C for 16 hours. The mixture was cooled with water and ether Diluted and filtered through glass fiber. The filtrate was extracted with ether, and the oil formed was distilled with celite (80-90 ° C, (U mm Hg), and recrystallized from hexane to give 3- (perfluoro- N-octyl) aniline (5.7 g, melting point 35.5-36. (:). 3- (perfluoro-n-octyl) aniline (2.04 g), 2,4-dinitrofluorobenzene (0.78 g) , NMP (8 ml) and triethylamine (0.85 ml), heated to 70 ° C for 16 hours. Extracted and recrystallized from hexane-ethyl acetate to obtain N_ [3- (perfluorooctyl) phenyl ] -2,4-Dinitroaniline (2.25 g, melting point 124.5-125 ° C). N- [3- (perfluorooctyl) phenyl] -2,4-dinitroaniline (5.4 g) , 3-bromopropene (1.5 ml), potassium carbonate (2.6 g), and N-methyltetrahydropyrrolidone (15 ml), heated to 60-70 ° C for 5.5 hours. Extracted in the usual manner, 5.6 G N-fluorenyl-N-[; H perfluorooctyl) phenyl] -2,4-dinitroaniline. N-fluorenyl-N- [3- (perfluorooctyl) phenyl ] -2,4-Dinitroaniline (6.3 g), a mixture of tin (II) gaseous dihydrate (19.8 g), 10 N hydrochloric acid (11 ml) and ethanol (75 ml), at 30-35 ° Treat for 6.5 hours at room temperature and overnight at room temperature. Dilute the mixture with water and make it 20 weight. Potassium hydroxide (180 g) is basified 'and extracted in the usual way, and purified by chromatography to give two Amine 5 (2.65 g, melting point 98-99.5 ° C). Example 6 The following example describes the synthesis of a novel aromatic diamine 6. 3-Perfluorooctylaniline (3.2 g), potassium carbonate (3.0 g), A mixture of NMP (30 ml of 0 and 3-bromopropene (0.67 ml), heated to 70-8 (rc after 3 Time. Extraction in a general way to obtain propyl-3-perfluorooctylaniline (1.7 g). ---- -29- Do not use the Chinese National Standard (CNS) A4 specification (21〇 297 without Am scale) (Mm) (Please read the notes on the back ^ Fill this page first) -Installation • i-rtr *-Printed by the Employees ’Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 561186 A7 B7 Printed by the Employees’ Cooperatives of the Intellectual Property Bureau of the Ministry of Economy Description of the invention (27) 2,4-dinitrophenol (4.6 g, 80% by weight), potassium carbonate (4.2 g), NMP (40 ml) and 1,4-dibromo-2-butane (12.8 G) mixture, heated to 45 ° C for 2 hours. Extraction in the usual manner and excess dibromide (0.1 mm Hg, 80 ° C) in crushed · algae soil to obtain 1-bromo-4- (2,4-dinitrophenyloxy) butane- 2-ene (3.7 g, melting point 55-57 ° C). N-allyl-3-perfluorooctylaniline (1.7 g), 1-bromo-4 · (2,4-dinitrophenyloxy) but-2-ene (1.08 g), NMP (20 ml) and potassium carbonate (1.5 g), heated to 80 ° C for 16 hours. The mixture was extracted in a general manner and purified by chromatography to obtain N- [4- (2,4-dinitrophenyloxy) but-2-enyl] -N-fluorenyl-3-all Fluoroctylaniline (0.75 g). In the usual manner, N- [4- (2,4-dinitrophenoxy) but-2-enyl] -N-allyl-3-h Reduction of fluorooctylaniline to provide diamine 6 0. Example 7 The following example describes the synthesis of a novel aromatic diamine 7. A mixture of 2,5-dinitrophenol (4.0 g), potassium carbonate (4.6 g), NMP (40 ml), and M-dibromo-2-butane (14.0 g) was heated to 45 ° C. 2 hours. Extraction in the usual way, and distilling excess dibromide (0.1 mm Hg, 80 ° C) with diatomaceous earth to obtain 1-bromo ice (2,5-dinitrophenyloxy) but-2-hydrazone ( Melting point 81-83X :). N-allyl-3-perfluorooctylaniline (1.7 g), bromo-4- (2,5-dinitrophenyloxy) but-2-fluorene (1.08 g), NMP ( Ml) and potassium carbonate (1.5 g), heated to 80 ° C for 16 hours. The mixture was extracted in a general manner and chromatographed to obtain N- [4- (2,5-dinitrophenyloxy) but-2_alkenyl]--30- _ paper Standards are applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) (Please read the notes on the back and fill out this page first) i Assembly line. 561186 A7 ---------- 5. Description of the invention (28). · N-allyl-3-perfluorooctylaniline. ♦ Reduct N_ [4_ (2,5-dinitrophenyloxy) but-2-fluorenyl] fluorenyl_3-perfluorooctylaniline in the usual way using gaseous tin hydrazone dihydrate To provide diamine 70. Example 8 The following example describes the synthesis of a novel aromatic diamine 8. A mixture of 3.17 g of bronze powder (Aldrich), perfluorosmall iodooctane (13.5 g), and dimethyamine (40 ml) passed through the steaming hall was heated to 1 (M20t for 30 hours, then Add 3-iodophenol (3.64 g). Stir the mixture at 100-110. (: Stir for 16 hours. Allow the mixture to cool, dilute with water and ether, and filter through glass fibers. Extract the filtrate in the usual manner, at room temperature The resulting oil was treated with potassium hydroxide (2.0 g) in methanol (30 ml) for 1 hour. The mixture was diluted with water, slightly acidified with 2 N hydrochloric acid, and extracted in the usual manner. The formed substance and hexane were purified by recrystallization to obtain 3- (perfluoro-n-octyl) pan. 3- (perfluoro-n-octyl) phenol (ι 24 · g), potassium carbonate (4.2 g), NMP (30 ml) and 1,4-dibromo-2-butene (12.8 g), heated to 45 ° C for 2N hours. Extracted in the usual manner and distilled with diatomaceous earth Excess dibromide (0.1 mm Hg, 80 ° C) to obtain 1-bromo-4-o (whole milk-n-octyl) phenoxy] but-2-ene. (1- Of 4- (3- (all-n-octyl) phenoxy] but-2-en (12.9 g) in tetrahydrofuran (20 ml), added to 40 wt% methylamine (20 ml), ethyl alcohol (20 ml) and tetrahydrofuran (20 ml) in a solution of 4 (TC. Stick the mixture at ambient temperature for 2 hours' and extract in the usual way. To treasure- 31-This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the note on the back ^: fill in this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by the Consumer Cooperative 561186 A7 2. Description of the invention (29) The oil formed by steaming the soil to obtain N_methyl (perfluoro_n-octyl) phenoxy] but-2-fluorenamine. N • methyl bucket [3- ( Perfluoro-n-octyl) phenoxy] but-2-enamine (5.96 g), 3-fluoro-4-nitroaniline (ι · 56 g), triethylamine (2.0 ml) and A mixture of NMP (15 ml) was heated at 80-90 ° C for 23 hours. The mixture was extracted in a general manner and purified by chromatography to obtain fluorenyl substituted nitronitroaniline. The above 3-substituted-4-nitro Aniline (7.3 mg) with gasification Compound (9.0 g), ethanol (80 ml) and ion hydrochloric acid (8 ml) were treated at 35-40 ° C for 18 hours. The mixture was diluted with water to 20 wt.% Potassium hydroxide (80 g) Alkalization, extraction in a general manner, and purification by chromatography to obtain diamine 8. Example 9 The following example describes the synthesis of a novel aromatic diamine 9. Copper powder (3.18 g, 50 mmol), A mixture of dimethylarsine (40 ml) and perfluoro-1-iodohexane (11.1 g, 25 mmol) was heated to 120 ° C for 1.5 hours. 4-iodoaniline (5.48 g, 25 mmol) was added, and the mixture was stirred at 110-120 C for another 5 hours. After quenching with water, the solid was filtered and extracted in the usual manner. This material was purified by chromatography to give perfluorohexylaniline (3.6 g). The mixture of 4-perfluorohexylaniline (3.6 g), tetrahydrofuran (40 ml), triethylamine (3.05 ml) and 2,4-dinitrofluorobenzene (1.63 g) must be refluxed for an hour. The mixture was extracted in a general manner, and the crude product was recrystallized to obtain king fluorohexyl) dongyl] -2,4-mononitrobenzylamine (3.8 g, melting point i45-146 ° C). · N- [4- (perfluorohexyl) phenyl] _2,4-dinitroaniline (3.6 g, 62 mmol), NMP (40 ml), potassium carbonate (3.0 g) And 3-bromopropene (〇 &amp; ml) (Please read the note on the back y ----- "Fill this page" &gt; aj.- Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ·

561186 A7 _ _____ B7 — Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (30) · Compound, stirred at 75 ° C for 4 hours. The mixture was extracted in a general manner, and the product was recrystallized to obtain N-allyl-N- [4- (perfluorohexyl) phenyl] -2,4-dinitroaniline (2.9 g). Add N · 晞 propyl-N- [4- (perfluorohexyl) phenyl] -2,4-dinitroaniline (2.9 g), ethanol (40 ml), 10 N hydrochloric acid (5.5 ml) and tin chloride (II) A mixture of dihydrate (10.0 g), heated to 35 ° C for 16 hours. The mixture was diluted with water to 20 weight. . Potassium hydroxide (90 g) was basified, extracted in the usual manner, and purified by chromatography to give diamine 9 (1.2 g, oil). Example 10 3,3 ·, 4,4 · -benzophenone tetracarboxylic dianhydride (3.69 g, 11.47 mmol), (N, N-diallylamino) -2,4-benzene A mixture of diamine (0.233 g, 1.15 mmol), diamine 1 (6.08 g, 10.32 mmol) and NMP (39.6 g) was stirred under nitrogen atmosphere at 18 ° C for 18 hours. The polyamic acid solution was diluted to 10 weight with butyrolactone (45.1 g) and NMP (5.03 g). . . For rotation, the polyamine solution was further diluted to 5 weights with a 50/50 r-butyrolactone / NMP solution. . . Spin coating on two 0.9-inch x 1.2-inch x 1-mm thick soda-lime glass substrates (DCI, Lenexa, KS 66219) with a transparent indium oxide-tin (ITO) coating Covering and curing to obtain an optical positioning layer. Spin coating was achieved by filtering the prepolymer solution through a 0.45 micron Teflon membrane filter onto the surface of a clean ITO substrate. The substrate was rotated at 2500 rpm for 1 minute to produce a uniform film. The formed film was aged at 80 ° C for 0.25 hours under nitrogen, and then at 80 ° C for 1 hour. · Figure 1 is a schematic diagram of an experimental apparatus for exposing a substrate. The laser beam with a diameter of about 1 cm from the laser 1 is polarized in the direction 2 and enters the polar pole -------- 33- _ (Please read the notes on the back first_fill this page) • The paper size of this paper applies the Chinese National Standard (CNS) A4 specification (210 X 297 public love) 561186 A7 V. Description of the invention (31) The combination of the rotator and the beam splitter 3, and when leaving, in its When propagating away from 3, it is separated into two polarized components 6 and 7. This laser has a wavelength range of 300-336 nm. By adjusting the polarization polarization rotator in 3, the ratio of the optical power in 6 and 7 can be adjusted, and in this case, the ratio is adjusted by Ma 1 6. The total power in 6 and 7 is about 500 mW. The mirror 5 will reflect 6 and 7 through the cylindrical lenses 8 and 9 and each has a focal length of 5 cm and 10 cm. After passing through the cylindrical lenses 8 and 9, 6 and 7 are focused on a line of about 1 cm x 0.2 cm on the substrate 10. The interval between two parallel focusing lines is about 1.5 mm. As depicted in Figure i, the substrate 10 is scanned with a vertical focus line. Because the length of the focus line of about 1 cm is smaller than the desired exposure area, after scanning once, the substrate is stepped by 1.5 mm perpendicular to the scanning direction (along the focus line). Repeat this step and scan u until the entire substrate area is exposed. The scanning speed for this exposure was 075 mm / sec. After the exposure, the substrates are assembled in the orthogonal orientation of the positioning directions generated optically. The cell thickness is about 4 microns. This cell is then capillary filled with a nematic liquid crystal suitable for an active matrix liquid crystal display. As expected: when viewing between polarizers, it was found that the liquid crystal walked in a twisted nematic orientation. 4 When the liquid crystal unit was tempered at the isotropic point of the liquid crystal (12 ° C, 30 minutes) It was found that the uniformity of positioning was improved and had good quality. The PAS-pre-tilt analysis system (service company, _ 抑 n, _ measures the pre-tilt, which is 19.6 degrees. Further tests using a scanning speed of 1.5¾ m / s, after tempering, resulted in 0.75 mm / Scanning speed is similar to the positioning quality in seconds. Read in pA ------------ install --- (please read the notes on the back first ^ fill this page) Printed by a cooperative

561186 A7 V. Description of the invention (32) The tilt analysis system (Elsicon, Wilmington, DE) measures the pretilt, which is 25.8 degrees. In another test, an Angstrom sdr printing machine (Kenix Industries, Tempe, AZ) from Nisshno Printing Co. was used, which would contain 52.6 weight by weight of 5 butoxybutanol. 4 Polymer solution is printed on the substrate. The printed substrate was exposed using the system of FIG. 1 at a scanning speed L5 mm / sec. After tempering, the positioning quality is similar to the previous test, and the pretilt is 96 degrees. Example 11: 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride (128 · 9 mg, 0.4 mol), (N, N-diaminopropylamino) -2 , 4-phenylenediamine (8.1 mg, 0.04 mmol), diamine 2 (203.8 mg, 0.36 mmol) &amp; NMP (1.36 *), stirred under nitrogen atmosphere at room temperature for 18 hours . The polyamic acid solution was diluted with butyrolactone (3.23 g) and NMP (1.87 g) to 5% by weight. A substrate was prepared, exposed at 0.75 mm / sec, and assembled as in Example 10. After tempering, the positioning quality is good, and the pre-tilt is 10 degrees. Example 12 3,3 ', 4,4'-benzophenone tetramethylene dianhydride (μm) mg, 0.50 millimolar, Ν, Ν- diallyl-1,2,4-phenyltriamine (10.2 mg, 0.05 mmol), a mixture of diamine 4 (267.8 mg, 0.45 mmol) and NMP (176 g) was stirred under nitrogen at room temperature for 18 hours. The polyamic acid solution was diluted to 5 weights with butyrolactone (418 g) and NMP (2.42 g). . . The substrate was prepared, exposed at 1.5 mm / sec, and assembled according to Example 10. After tempering, the positioning quality was good, and the pretilt was 21.7 degrees. Example 13 -35- This paper rule ^ applies Chinese National Standard (CNS) A4 specification (21〇X 297 public love) -------- (Please read the note on the back first to fill in this page) -Line. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 561186 A7 V. Description of the invention (33). 3,3 ', 4,4, -benzophenone tetracarboxylic dianhydride (128.9 mg, 0.40 mmol) Mol), Ν, Ν-diallyl-1,2,4-phenyltriamine (8.1 mg, 0.04 mmol), diamine 5 (236.6 mg, 0.36 mmol) and NMP (1.48 G), and the mixture was stirred at room temperature under a nitrogen atmosphere for 18 hours. The polyamic acid solution was diluted with butyrolactone (3 52 g), NMP (2.04 g) and ethylene glycol monobutyl ether (5.04 g) to a weight of 3/0. A substrate was prepared, exposed at 1.5 mm / sec, and assembled as in Example 10. After tempering, the positioning quality was poor to normal, and the pre-tilt was 3.5 degrees. (Please read the notes on the back first and fill in this page) Packing-line · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -36 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

Patent application No. 21950 as amended version of patent scope (May 91), VI. Patent scope 91 · 5 · 14 years A _-ι · A kind of polyimide, polyamic acid and its esters The reactive side chain polymer in is characterized in that it includes a monovalent side chain of the general formula I: -Lj -D-L2 -Cf I wherein the monovalent chain is bound to the polymer main chain, and wherein: Li and L2 each Independently a covalent bond or a linking group, selected from -〇-, _ 孓, -NRi- ^ -O-CO- &gt; -CO-0- &gt; -NRj-CO---CO-NR!-- -NR ^ CO-O-, -O-CO-NRr, -NRi-CO-NRr, and linear and branched chain alkylene groups, with-(CH2) n-, -L3- (CH2) n-, -(CH2) n-L3-, _L3- (CH2) n-L4- indicates that each is mono- or poly-substituted by fluorine or chlorine, and is optionally inserted by -NRi-, where L3 and l4 are Selected from -O-, _S-, -NRi-^ -O-CO- &gt; -CO-O- '-NR! -C〇. ^ -CO-NR!-&Gt; -NR ^ CO-O-' -O- CO-NR!-, -NRi-CO-NRi-, the core is hydrogen or a lower alkyl group, and n is i to 20; D is a divalent group containing 1 to 4 carbon-carbon double bonds , Selected from C3 &lt;: 24 aliphatic, GC: 24 cycloaliphatic, C8-C24 aralkyl, all of which are 4 heteroatoms selected from the group consisting of oxygen, nitrogen and sulfur, and optionally substituted by fluorine, milk or amino early or more 'where the carbon-carbon double bond system is isolated from any other Π-system in the side bond; cf represents unit price c4 to c20 fluorocarbon groups. 2. If the side chain polymer in item 1 of the patent application scope, wherein the polymer main chain contains the same or different repeating units, selected from one or more of the following chemical formulas, this paper applies Chinese National Standard (CNS) A4 specifications (210 X 297) (Mm) 186 Patent Application Range 〇 Ο Ν Μ Να · Ila ο δ Cf ο ο ΝΗ 一 A- lib L "D-L ^ Cf, which is a tetracarboxylic dianhydride in the form of removing two seven a0_c〇_ groups of tetravalent organic groups, whose four valence bonds are distributed in the group The four different groups are: ，, 子, and ；; A is trivalent unsubstituted, or optionally fluorine, chlorine *, cyano_, alkyl_, alkoxy_, fluoroalkyl- or fluoroalkoxy Aromatic or cycloaliphatic radicals substituted by a radical; and B is hydrogen, or a monovalent organic radical derived from an alcohol after the hydroxyl group has been formally removed. 3. A side chain polymer such as the item 2 of the scope of patent application, wherein M is (¾ where X is independently selected from Η, Cl, F, Br, and CF3; Z is selected from -S-, -0-, -S02-, -CH2-, -C (CF3) 2-, -C (0 )-, _CH2〇V, -NRi-, and covalent bonds, where Ri is selected from H or lower alkyl groups; m is 1 or 0; and A is selected from -2 This paper is applicable to Chinese National Standards (CNS) A4 specification (210 X 297 mm) 561186 A8 B8 C8 D8 Patent application scope And fluorenyloxy. 4. The side chain polymer according to item 3 of the application, wherein D is selected from —C ^ CHCH— —Cf ^ CHCHCH ^ — CH2CH = CHCH2- 5. If the side chain polymer of item 4 of the patent application scope, wherein the polymer main chain contains the following repeating units 6. A liquid crystal display, which is made of an optical positioning layer derived from a side chain polymer of item 1 of the scope of patent application. 7. A liquid crystal device other than a display, which is made of an optical positioning layer derived from the side chain polymer of the first patent application. -3- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)